Maleic acid and furfural ketone reaction products



MALEIC ACID AND FURFURAL KETONE REACTION PRODUCTS Peter L. Rosamilia, Newark, N. J., assignor to Harvel Research Corporation, a corporation of New Jersey No Drawing. Application April 20, 1955 Serial No. 502,720

15 Claims. (Cl. 260-63) This invention relates to novel methods for producing resinous reaction products and to the novel products produced thereby as well as to novel compositions in which said novel products are components. In one of its more specific aspects, the invention is directed to novel resinous reaction products of maleic acid and furfural ketone reaction products and derivatives thereof.

Among some of the ketones which may be employed to produce said furfural-ketone reaction products are those having two hydrogen atoms on an alpha carbon, examples of which are acetone, methyl ethyl ketone, methyl iso-butyl ketone, diacetone, alcohol, mesityl oxide, isophorone, cyclohexanone, phorone, acetophenone, methyl-n-amyl ketone, acetonyl acetone (hexandione 2, 5), diethyl ketone, di-iso butyl ketone, etc. By maleic acid as employed herein I mean either maleic acid or its anhydride.

The furfural-ketone reaction products may be produced by following the procedure known to the art by reacting under alkaline conditions, furfural with one or a com bination of two or more of said ketones to produce an organic reaction mass having a quantity of resin therein measuring at least 5% by weight of the organic reaction mass. Generally, the furfural and ketone are mixed with each other and then there is added thereto a quantity of an alkaline material such as an aqueous solution of sodium hydroxide, potassium hydroxide, lime or the like. These three components are mixed with each other in an autoclave or closed unit and in most cases after the mixture takes place, an exothermic reaction occurs and the pressure within the autoclave will rise. After the, exothermic reaction has subsided, the initial reaction is practically complete. In order to assure complete reaction and high yields, the mass in the autoclave is externally heated to maintain it in the state of boiling for a period of time depending upon the viscosity desired of the resultant organic-reaction mass which may vary from a fairly thin liquid to a solid at room temperature. The viscosity of the organic reaction mass after dehydration is at least 50 cps. at 25 C. and in all cases the organic reaction. mass is a liquid at 250 F.325 F.

These furfural-ketone reaction masses which when dehydrated are liquid at 250 F.325 F. and for some purposes I prefer to employ those which have a viscosity between about 50 and 20,000 cps. at 25 C. and in all instances contain compounds which are either mono and combination of mono and difurfurylidene ketones and/ or polymers thereof, said compounds having the following formulae:

United States Patent 0 ice oxygen of the furfuraldehyde to split off water. This reaction also provides an amorphous or resinous material. The quantity of said resinous material present in all of the reaction masses varies and is dependent upon the time magnitude of boiling of the reaction mass and is approximately 5% or more of theorganic reaction mass by weight and in generalmeasures about 5%80% by weight of the organic reaction mass when in liquid condition.

The following specific example for producing the furfural-ketone reaction mass, which will be identified herein as product A, is given merely by way of illustrating in general a method for producing the furfural-ketone reaction masses, and also shows various fractions or other reactants which may be obtained therefrom.

Example A Into a one-gallon pail is placed a quantity of sodium hydroxide weighing 2 lbs. 6 oz. Then there is added thereto sufiicient water to fill the pail and the sodium hydroxide in the water is stirred until the sodium hydroxide is completely dissolved therein. Then in a Monel metal-lined autoclave are placed 40 lbs. of furfuraldehyde and 24 lbs. of acetone. This autoclave is preferably provided with a mechanical agitator or stirrer which may be in the nature of a paddle mixer. This mixture is agitated and while in the state of agitation there is added thereto about /6 of the volume of said heretofore prepared aqueous solution of sodium hydroxide. With all tion of the sodium hydroxide solution and the temperature of the mass continuously agitated by the stirrer will rise to approximately F. in about 3 or 4 minutes. After about 10 minutes there is added to the mass in said autoclave another charge consisting of 40 lbs. furfuraldehyde. and 24 lbs. acetone. Then to the mass is added a second increment of said sodium hydroxide solution equal in volume to the first addition. After a few minutes the temperature of the mass, due to the exothermic reaction, will rise to approximately l70 F. The foregoing steps are. repeated four more times so that the amount of furfuraldehyde and'acetone added to the autoclave are equal to 240 lbs. and 144 lbs; respectively, and all of the initially prepared aqueous solution of sodium hydroxide has been added. After the last addition of. sodium. hydroxide the temperature of the mass within the autoclave will have stabilized to about ISO-195 P. Then the mass within the autoclave may be heated by means of a steam coil located therein and through a jacket carried thereby to maintain the temperature of the mass between approximately l85195 F. for about 30 minutes in order to complete the reaction and to obtain high yields. The steam is cut off from the coil and jacket and then there is added thereto an aqueous solution of sulphuric acid in quantity sufiicient to render the mass practically neutral. In this instance there may be added an aqueous solution of sulphuric acid consisting of 3 lbs. 3 OZ. of concentrated sulphuric acid diluted in 6 lbs. 6 oz. of Water. Then this mass may be heated for about 5 minutes at a temperature between -200 F. to substantially completely neutralize the mass. The substantially completely neutralized mass may then be substantially completely dehydrated by heating the same to. a temperature of 220 F. with or Without vacuum yielding approximately 300 lbs. of'dehydrated substantially neutral material known as product A, whose viscosity at 25 C. is 92 cps. and having a specific gravity of 1.150 at 25 C.

When product A is distilled at a pressure of approximately 0.1 mm. of mercury pressure, a fraction (37%) weighing approximately 110 lbs. .comes off at a temperature in the range of 70 C.-85 C., is essentially monofurfurylidene-acetone and i hereinafter known as product A-l and leaving a residue known hereinafter as product R-I. A second fraction (47%) measuring approximatelv 140 lbs. comes off in the tem erature range of 150 C.-l 66 C., is essentially difurfurylidene-acetone and is hereinafter known as product A-II. The residue measuring approximately 50 lbs. is a brittle solid on cooling to room temperature and at 325 F. is liquid. Analysis of product A-I established a carbon content of 70.30% and h drogen of 5.48% which corresponds to the carbon and hydro en values of monofurfurylidene-acetone having the following formula:

A number of other specific examples for the production of these various furfural-ketone reaction masses and fractions such as products A-I, A-II and R-I may be found in U. S. Patent No. 2,516,317, issued July 25, 1950, as well as in the first part of Examples 1-20 in U. S. Patent No. 2,363,829, issued November 28, 1944, and the first part of Examples 1-16 of U. S. Patent No. 2,461,510, issued February 15, 1949.

These various (a) furfural-ketone reaction masses, (b) residues of said masses produced by the heat distillation thereof and measuring by weight at least approximately and generally approximately %-95% and preferably at least 60%. of said masses, (c) monofurfurylidene ketone, (d) difurfurylidene-ketone, and (e) homopolymers of (a), (b), (c) and (d) respectively may be employed as the reactants in the practice of this invention and in all cases, said reactants (a)-(e) respectively are liquid at 325 F. Said (a)-(d) res ectively may be homopolymerized in a number of difierent ways: For example. by heating them at elevated temperature of about ISO-260 F. in factory practice while in the presence of an acidic or alkaline agent or catalyst, such as diethvl sulphate, sulphuric acid, hydrochloric acid, phosphoric acid. zinc chloride, boron trichloride or the like, sodium hydroxide, potassium hydroxide, lime, sodium carbonate or the like. When such homopolymerization is conducted under acidic conditions, the amount of acidic catalyst employed is such that the pH of the mix is between approximately .35 and 3 and for most purposes in the range of .51.5; when such homopolymerization is conducted under alkaline conditions, the amount of alkaline catalyst employed is such that the pH of the mix is at least 8 and for most purposes in the range of about 8.5-13. A specific method, given merely for the purposes of illustration, which may be employed to produce said homopolymers of (a)-(d) respectively is to charge a quantity of any of them into a container and then there is added thereto a quantity of catalyst either alkaline or acidic to impart a pH to said mix within the ranges heretofore set forth. Then such mix is maintained at approximately 250 F. until a solution of the resultant homopolymers in an equal weight of acetone has a viscosity centipoises at 25 C. at least 100% greater than that of a solution of the corresponding original product (a)-(d) respectively in an equal weight of acetone. These homopolymers of (a)(d) are in all cases liquid at 325 F.

Other reactants which may be employed in the practice of this invention are (a)-(e) respectively which have been partially hydrogenated by employing the procedure set 4 forth in the U. S. patents to M. T. Harvey, 2,600,403 and 2,600,764, both issued June 17, 1952, which patents in their entirety are made part hereof. In general for partially hydrogenating said (a)-(e) respectively, I prefer that they first be rendered substantially neutral and completely dehydrated.

These substantially neutral, completely dehydrated materials may then be hydrogenated only partially by employing a nickel catalyst, maintaining the temperature at a value of C. and preferably in the range of 120 C.250 C. and the pressure thereof at a value of 25 lbs. per sq. in. and between 25-250 lbs. per sq. in. but preferably between 30-75 lbs. per sq. in. The nickel employed is in a finely divided state and may be coupled with a suitable carrier such as hydrogenated vegetable oil, hydrogenated cardanol, etc.

Briefly, the hydrogenation may be accomplished by adding the requisite amount of nickel catalyst in the carrier to said dehydrated approximately neutral material and the mixture is heated While vacuum is applied and agitated until a uniform mixture has been obtained. When the temperature of the mix reaches 120 C. the external source of heat is removed, hydrogen gas is admitted thereto to provide a pressure of 25-250 lbs. per sq. in. whereupon hydrogenation takes place and is an exothermic reaction. The addition of the hydrogen is continued whereupon the temperature of the mass rises and is maintained at a level no greater than 250 lbs. per sq. in. and generally between 30-75 lbs. per sq. in.

The hydrogen is continuously added under the'aforesaid conditions until the amount of added hydrogen per 40 lbs. of said material is approximately 70-340 cu. ft. measured at 20 C, and 760 mm. pressure. The hydrogen added is approximately 15%-65% of the quantity of hydrogen necessary for complete saturation of all the carbon to carbon double bonds thereof. The hydrogenation is discontinued after the desired degree of hydrogenation has been attained. Then the hydrogenated material is allowed to cool to room temperature. By this procedure the material after hydrogenation is stiH unsaturated. The carbon to carbon double bonds of the compounds in said material and outside of the furane ring have been at least 50% saturated with hydrogen, and may be 50%-100% saturated with hydrogen, with 0%-50% saturation with hydrogen of the carbon to carbon double bonds in the furane ring.

When the material to be hydrogenated is of a very high viscosity, for example over 20,000 cps. at 25 C., I first dissolved the mass in a solvent, such as a high molecular weight ketone, and then hydrogenate under the aforesaid conditions.

The following examples illustrate methods for producing the partially hydrogenated furfural-ketone reaction masses, residues and fractions thereof, which fractions may be mono-furfurylidene-ketone and difurfurylideneketone, examples of which are product A-1 and product A-II, and also said homopolymers thereof.

Example B 40 lbs. of product A is placed in a 10-gallon closed unit equipped with a high speed propeller. Then l-lb. of a catalyst and carrier combination containing 25% of catalytic nickel dispersed in a hydrogenated vegetable oil is added thereto and the mixture is continuously stirred in order to maintain a uniform distribution of the components. While in this state of agitation, the mass is externally heated to a temperature of 120 C. after substantially all the air in the container has been evacuated therefrom. Then hydrogen is admitted to provide a pressure of 40 lbs. per sq. in. Hydrogen is continuously admitted to the mass and hydrogenation takes place exotherrnically and now the external source of heat is removed therefrom. By controlling the speed of addition of the hydrogen to the mass, the temperature is maintained at approximately 200 C. and the pressure of approximately 50 lbs. per sq. in. The temperature during hydrogenation may also be controlled by external cooling. The hydrogen addition is terminated when no more hydrogen is taken up under these conditions with aperiod of about 30 minutes.

The quantity of hydrogen taken up in this particular hydrogenation step apparently due to early poisoning of the catalyst amounted to approximately 145 cu. ft. which corresponds roughly to the quantity of hydrogen required to saturate only the unsaturated carbon to carbon atoms outside of the furane ring. The same procedure may be followed with product R-l to partially hydrogenate it to the same extent as product A, and such partially hydrogenated product R- I is hereinafter referred to as HR-I. The same proceduremay also be followed with products A l, A-II and R4 respectively, which have been homopolymerized to such a'degree that a solution thereof in an equal weight of acetone has a viscosity in centipoises at 25 C. equal to 200% that of a like solution of corresponding original product employed to provide partially hydrogenated products hereinafter known as products I-IPA, HPA-I, HPA-II and HPR-I.

This hydrogenated product A, known hereinafter as product B, is still a thin liquid and may be distilled if desired to separate various fractions thereof. By distilling this hydrogenated product B at 0.3 mm. of mercury pressure a fraction distilled off up to 100 C. and

was collected and amounted to 32%; a second fraction amounting to 41% distilled off and was collected at 120- 170' C. That fraction which distilled off up to 100 C. is hereinafter known as fraction B-1 and consisted essentially of a compound having the following formula:

The second fraction'which distilled off at l20l70 C. is hereinafter known as fraction B-'-2 and consisted essentially of a compound having the following formula:

The residue known as B-3 upon cooling was a brittle black solid at room temperature.

Example C By using the same procedure as that set forth in Example A and substituting 180 lbs. of methyl ethyl ketone for the 144 lbs. of acetone and then hydrogenated according to Example B, terminating the hydrogen addition when approximately 150 cu. ft. of hydrogen have been taken up, there may be produced a novel hydrogenated product known hereinafter as product C. Product C may be distilled to provide fractions C-1 and C-2 respectively, chiefly consisting of the following compounds:

and a resinous residue O-3 of more than 5% of the hydrogenated mass.

Example D By using the same procedure as that set forth in Example C and substituting 240 lbs. of diacetone alcohol for the 180 lbs. of methyl ethyl ketone, there may be produced a novel hydrogenated product known as product D. This hydrogenated product D may be distilled to provide fractions D-1 and D-2 respectively consisting chiefly of the following compounds:

and a resinous residue D-3 of more than 5% of the hydrogenated mass.

Example E Following the same procedure as that set forth in Example B- and using fresh catalyst and terminating the hydrogenation after approximately 70, 100, 150, 175, 210 and 235 cu. ft. of hydrogen were taken up in six different 40 lb. batches of product A, I obtained products E-I,

E-2, E-3, E-4, E-S and E-6, differing from each other in the degree of hydrogen saturation.

Example F Following the same procedure as that set forth in EX- ample B and employing fresh catalyst, 235 cu. ft. of hydrogen were taken up in a 40 lb. batch of product A. Then the same amount of fresh catalyst, .25 lb. powdered nickel, was added thereto and hydrogenation continued until a total of 340 cu. ft. of hydrogen was taken up. This product is known as product F.

Example G Following the same procedure for hydrogenating as that set forth in Example B and employing product A-I in place of product A and terminating the hydrogenation after 1.3 and 1.8 moles proportionately of hydrogen were taken up by 1 mole proportion of said fraction, approximately and cu. ft. of hydrogen per 40 lbs. of

product A-I. The hydrogenation above the 1.3 moles proportion proceeded .with difficulty. These two hydrogenated products are G-1 and G-2 and were respectively about 43% and 60% hydrogenated at the carbon to carbon double bonds.

Example Examples I-K Employing the same procedure as that set forth in Example B and employing respective residues measuring by weight about 60% of product A, furfural-methyl ketone reaction mass of Example C, furfural-diacetone alcohol reaction mass of Example D, there were obtained respec-- tive partially'hydrogenated products I, J and K.

Said partally hydrogenated products, examples of which are illustrated in Examples A-K may be respectively homopolymerized or thickened and such homopolymers may also be used as reactants in the practice of this invention. Said homopolymerization or thickening may be effected by the use of an acidic catalyst, generally with the use of heat. Any of the acidic catalysts may be employed for this purpose and for most purposes in amount sufficient to provide a mix having a pH no greater than 4 and for most purposes .3-3. While under the lower pH conditions the homopolymerization may proceed at room temperature, it is preferable that external heat be used and the high pH, for example 180-450 F. and pH about 2-2.5.

In any case, the acid catalyzed mass is maintained within said temperature range until the polymerization or thickening has reached the desired degree as evidenced by an increase in viscosity which in all cases is at least 100% greater than the viscosity of the material treated before polymerization or thickening. In all cases, the heat is removed so that all of the acid polymerized materials so produced are preferably liquids or pourable at room temperature and in any event are liquid at 325 F., that is to say, that the heat is removed before any of them is converted to the solid infusible state and all of these products will hereinafter be known as acid-polymerized materials. Various specific examples of said acid polymerized unhydrogenated materials in the liquid state at room temperature may be found in said U. S. Patent 2,461,510 and other examples of said polymerized unhydrogenated materials may be found in U. S. Patent 2,516,317, reference is hereby made to said printed publications.

Reference is also made to said Patents 2,600,403 and 2,600,764 showing various liquid acid polymerized hydrogenated materials liquid at 325 F. examples of which are as follows:

Example L All of the various specific hydrogenated products hereinbefore disclosed were separately mixed with diethyl sulfate in the proportion of 10-40 cc. of the latter for each 6 lbs. of the former, the quantity of diethyl sulfate employed being greater when employed with the more highly hydrogen saturated products. In factory practice, 10 cc. of diethyl sulfate was employed with those products which took up 150 cu. ft. of hydrogen per 40 lbs., 20 cc. of diethyl sulfate for those which took up 150-250 cu. ft. of hydrogen per 40 lbs. etc. Each mixture was heated and while being continuously stirred was maintained at a temperature of 260-325 F. whereupon an exothermic reaction took place and the mass thickened rapidly. When the mass has attained the desired viscosity in the course of this exothemic reaction it is rapidly cooled in any convenient manner to stop the reaction. The reaction is preferably stopped at that stage of polymerization where the product is a liquid resin capable of being converted to the solid state upon extended heating at 300 F. and has a viscosity at 25 C. of at least 100% greater than that of the unthicknened product, or if the partially hydrogenated product is a solid, polymerization is stopped when a 50% acetone solution thereof has a viscosity at 25 C. about 200% of that of a like solution of said product before polymerization.

According to this invention novel reaction products, either in the liquid or the solid state, may be produced by reacting (I) maleic' acid and (II) material liquid at 325 F. and selected from the group consisting of (a) organic reaction masses produced by reacting furfuraldehyde and a ketone having at least two hydrogen atoms on an alpha carbon, at least by weight of each of said reaction masses being a resinous material; (b) residues of (a) produced by heat distillation of (a) and measuring by weight at least and preferably 60% of (a); (c) monofurfurylidene ketone; (d) difurfurylidene ketone; (e) homopolymers of (a)(d) respectively; (1) partially hydrogenated homopolymers (e), reaction masses (a) and residues (b); (g) partially hydrogenated monofurfurylidene-ketone; (h) partially hydrogenated difurfurylidene-ketone; (i) residues of partially hydrogenated (a), said residues produced by the heat distillation thereof and measuring by weight at least 10% and preferably at least 60% thereof; (j) homoploymers of (f)-(i) respectively, said (f), (g) and (h) produced by partially hydrogenating materials (a)(e) respectively to saturate them with hydrogen to the extent equal to approximately 15%- 65% of that required to saturate all of the carbon to carbon double bonds in said materials (a)(e). Examples of some of said materials (11) are products A, A-I, A-II, R-l as well as said products homopolymerized and the partially hydrogenated products, examples of which are disclosed in Examples B-K and the homopolymers thereof, with all of the foregoing materials being liquid at 325 F, and all of said materials (II) may be employed alone or in combination of two or more of them in the reaction with maleic acid. In general this reaction is carried out by heating a mixture thereof in the following ratio range by weight of the former to the latter: 20-1 to 10-4. This mixture is heated. and maintained at a temperature of 250-400 F. to provide resinous reaction products, known hereinafter as product (X) which may be either in the liquid or solid state depending upon the degree and time of heating and in the solid state may be converted to the liquid state at 300 F. Thus a variety of different products (X) may be produced depending upon the reactant employed with maleic acid.

While these various products (X) find utility in the liquid state, these products are of particular significance in their solid state because in that state they are hard materials which can be readily ground into a powder which will not mass and consequently find utility as components in molding powders. Products (X) may also be converted to the solid infusible state by heating at a temperature between 250-300 F. under acidic conditions such that the pH is no greater than 3.5. Said products X may also be acid polymerized to provide thickened or polymerized products in the intermediate state. These thickened or polymerization products are capable of being reacted with a reagent containing a reactive methylene group.

Products (X) as well as said acid polymerization products thereof in the intermediate state, which in factory practice are produced at a pH no less than 1.0 may be reacted on either the acid or alkaline side with one of said reagents in the ratio range of -2 to 100-l0 to provide solid infusible resins. I prefer, however, to carry out this reaction on the alkaline side because it proceeds much faster on the alkaline side. Among some of said reagents which may be employed are hexamethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein, acetaldehyde, etc. and I employ any of the alkalies such as sodium hydroxide, lime, etc., for maintaining the mass on the alkaline side. The following are certain specific examples merely for the purpose of illustrating the methods for providing some of the various products of the invention.

Example 1 100 parts by weight of product A and 20 parts of maleic anhydride are mixed and the solution is heated to about 300 F. and maintained at this temperature for a period of approximately 1 to 2 hours. The heating is stopped when a sample thereof cooled to room temperature is a hard brittle solid. At this state the mass is rapidly cooled to room temperature and at that temperature is a hard brittle solid known as product 1.

Example 2 Following the same procedure as that set forth in Example 1 and employing a furfural-mesityl oxide reaction mass (produced in accordanre with the general method set forth in Example.A) instead of product A, there was produced a hard sold resinous reaction product known as product 2.

Example 3 Employing the same procedure as that set forth in Example 1 and substituting the furfural-acetonyl acetone reaction product made in accordance with the first part of Example 1 of U. S. Patent 2,156,317 for product A, there was produced a hard solid brittle resinous reaction product hereinafter known as product 3.

Example 4 Following the same procedure as that set forth in Example 1 and employing 100 parts of a liquid acid or alkali polymer of product A in place of product A, the viscosity of said polymer being fifty times that of product A, there was produced a solid brittle resinous reaction mass known as product 4.

Examples 5-60 Examples 61-68 Employing the same procedure as that set forth in Example 1, except for product A therein, substitute respectively products A-I, A-II, R-I and homopolymers, produced under either alkaline or acidic conditions, of A-I, A-II, R-I, furfural-mesityl oxide reaction masses and of furfural-methyl ethyl ketone reaction masses polymerized to such a degree that a solution thereof in an equal Weight of acetone has a viscosity in centipoises at 25 C. about 300% that of a solution of the corresponding reaction mass in its original condition. The resultant reaction products were resinous solids at room temperature and are known as products 61-68.

Example 69 Employing the same procedure as that set forth in Example 1 but instead of product A, an acid polymerized product, product B having a viscosity at 25 C. fifty times that of the original product B, there was produced a solid brittle resinous reaction mass known as product 69.

Examples 70-74 Employing the same procedure as that set forth in Examples 14 and 69 except that the reactants are maintained at 300 F. for a much shorter period of time, namely, in the range of 15-30 minutes there are produced reaction products which are liquid at room temperature and known as products 70-74.

Examples 75-] 1 Employing the .same procedure as that set forth in Example 70 except for product A there is substituted the respective products B, B-l, B-2, C, C-l, C-2, D, D-l, D2, E-l to E-6, F, G-l, G-2, H-l to H-4 and the polymers thereof .whose viscosity in centipoises at 25 C. are 250% that of the unpolymerized corresponding material, to obtain liquid reaction products resinous in nature and known as products ,75-118.

Example 119 Solid resinous reaction product 119 was obtained by employing the same procedure as that set forth in Example 1 but instead of product A, there was used: Product A which has been (1) homopolyrnerized under either alkaline or acidic conditions so that the viscosity thereof at 25 C. is about 200 centipoises, then (2) this homopolymer was hydrogenated so that 20% of the carbon to carbon double bonds therein were saturated with hydrogen and subsequently (3) said partially hydrogenated product was homopolyrnerized under acidic conditions so that its viscosity increased to 600 cps. at 25 C.

All of these maleic acid resinous reaction products, examples of which are the illustrative products l-119, are compounded with various (III) normally solid rubbery materials, such as natural rubber, homopolymers of butadiene, copolymers of butadiene and styrene, copolymers of butadiene and acrylonitrile and polymers of chloroprene to improve their impact, oil resistance and ozone resistance and also their ageing characteristics. The same procedure may be followed as is followed in the normal milling or other type of mixing used for such products (III) and the various accelerators, vulcanizers, fillers, etc. may be employed as is known to the art. The ratio of one or more products l-119 to the material (III) is preferably in the range of 2 parts of the former to 1-200 parts of the latter. and upon further heating at 300 F. may be converted to the state wherein at room temperature they are solid and products 1-69 and 119 at room temperature are solid and brittle and capable of liquification at 300 F. They, all, whether in the solid or liquid state, find utility in a variety of different fields when used either alone or in combination or reacted with other materials. They all find utility as components of molding composition and products 169 and 119 especially in molding powders. They all find utility as binders for brake linings and clutch facings either alone or reacted with said reagents; also by themselves or their reagent containing reaction products employed as binders in grinding wheels; and also as binders for locking fibers such as paper fibers to each other either en masse or in lamination. The liquid products 70-118 especially and also products l-69 find utility in the production of rubbery materials.

The following are certain specific examples given merely for the purpose of illustrating the method for providing the solid infusible resins of the invention.

Example 120 parts of products 1-119 were mixed with 5 parts of hexamethylene tetramine. The mixture was heated and maintained at a temperature of 250350 F. for about 10-20 minutes to provide solid infusible resins.

Example 121 100 parts of any or a combination of two or more of products l-1l9 were mixed with 5 parts of lime, 6 parts of diethyl sulphate and the mixture was heated and maintained at a temperature of 250350 F. for 10-20 minutes to provide solid infusible resins.

Example 122 100 parts of any one or a combination of two or more of products 1-69 and 119 is heated and held at 250 F. to liquify. Then there is added 6 parts of paraform and 5 parts of diethyl sulphate and the mixture maintained at a temperature of 250350 F. for about 15 minutes to provide solid infusible resins.

Example 123 Products 70-118 are liquid cardanol-aldehyde, residues of cashew nut shell liquidaldehyde, either of a thermoplastic nature or of a thermosetting nature in their intermediate state, in the approximate proportions by weight of 9 parts of product X to 190 parts of any one or a combination of two or more of said resins, either with or Without a quantity of Vinsol or Vinsol-aldehyde resin measuring 550% of the combined weights of said product X and said resinous combination of resin. These various combinations also find utility in the art of clutch facings, brake linings, and other friction elements as well as in the field of hinders in the art of grinding Wheels, sand paper and in the matted fiber arts.

Since certain changes in carrying out the aforesaid processes and certain modifications in the composition which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

This application is a continuation-in-part of my copending application Serial No. 358,197, filed May 28, 1953, and since abandoned, which was a continuation-inpart of my application Ser. No. 191,935, filed Oct. 24, 1950, and now abandoned.

I claim:

1. A resinous reaction product produced by heat reacting (I) maleic acid and (II) material liquid at 325 F. and selected from the group consisting of (a) organic reaction masses produced by reacting furfuraldehyde and a ketone having at least two hydrogen atoms on an alpha carbon, at least 5% by weight of each of said reaction masses being a resinous material, (1)) residues of (a) produced by heat distillation of (a) and measured by weight at least of (a), (c) monofurfurylideneketone, (d) difurfurylidene-ketone, (e) homopolymers of (a)(a') respectively, (1) partially hydrogenated homopolymers (e), reaction masses (a) and residues (12), respectively, (g) partially hydrogenated monofurfurylideneketone, (h) partially hydrogenated dlfurfurylidene-ketone, (i) residues of partially hydrogenated (a), said residues produced by the heat distillation thereof and measuring by weight at least 10% and preferably 60% thereof, (j) homopolymers of (f)--(i) respectively, said (f), (g) and (h) produced by partially hydrogenating materials (rz)- (e) respectively to saturate them with hydrogen to the extent equal to approximately 15%65% of that required to saturate all of the carbon to carbon double bonds in said materials (a)(c).

2. A resinous reaction product defined in claim 1, said product being in the solid state at room temperature.

3. A resinous reaction product produced by heat reacting (I) maleic acid and (II) difurfurylidene-ketone.

4. A resinous reaction product produced by heat reacting (I) maleic acid and (II) homopolymerized difurfurylidene-ketone, said (II) being liquid at 325 F.

5. A resinous reaction product produced by heat reacting (I) maleic acid and (II) difurfurylidene-ketone which has been saturated with hydrogen to the extent of approximately 15 %65 of the carbon to carbon double bonds therein.

6. A resinous reaction product produced by heat reacting (I) maleic acid and (II) homopolyrnerized difurfurlidene-ketone which has been saturated with hydrogen to the extent of approximately 15 %65 of the carbon to carbon double bonds therein, said (II) being liquid at 325 F.

7. A resinous reaction product produced by heat reacting (I) maleic acid and (II) an organic reaction mass produced by reacting furfural and a ketone having two hydrogen atoms on an alpha carbon, at least 5% by Weight of said mass being a resinous material.

8. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paraformal- 12 dehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a resinous reaction product as defined in claim 1.

9. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a res inous reaction product as defined in claim 2.

10. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexarnethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a resinous reaction product as defined in claim 3.

11. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehye and (III) a resinous reaction product as defined in claim 4.

12. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paratormaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a resinous reaction product as defined in claim 5.

13. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a resinous reaction product as defined in claim 6.

14. A resinous reaction product produced by heat reacting (IV) a material selected from the group consisting of hexamethylene tetramine, formaldehyde, paraformaldehyde, trioxane, glyoxal, polymerized glyoxal, acrolein, polymerized acrolein and acetaldehyde and (III) a resinous reaction product as defined in claim 7.

15. The method for producing a resinous reaction product comprising heat reacting (I) maleic acid and (II) material liquid at 325 F. and selected from the group consisting of (a) organic reaction masses produced by reacting furturaldehyde and a ketone having at least two hydrogen atoms on an alpha carbon, at least 5% by weight of each of said reaction masses being a resinous material, (b) residues of (a) produced by heat distillation of (a) and measuring by weight at least 10% of (a), (c) monofurfurylidene-ketone, (d) difurfurylideneketone, (e) homopolymers of (a)-(d) respectively, partially hydrogenated homopolymers (e), reaction masses (a) and residues (b) respectively, (g) partially hydrogenated monofurfurylidene-ketone, (h) partially hydrogenated difurfurylidene-ketone, (i) residues of partially hydrogenated (a), said residues produced by the heat distillation thereof and measuring by Weight at least 10% and preferably thereof, (j) homopolymers of (f)(i) respectively, said (f), (g) and (h) produced by partially hydrogenating materials (a)(e) respectively to saturate them with hydrogen to the extent equal to approximately 15 of that required to saturate all of the carbon to carbon double bonds in said materials References Cited in the file of this patent UNITED STATES PATENTS 2,363,829 Caplan et al Nov. 18, 1944 2,461,510 Harvey Feb. 15, 1949 2,751,084 Harvey Oct. 16, 1951 OTHER REFERENCES Alder et al.: Ber. der Deut. Chem. GeseL, vol. pages 183, 186 and 194-196. 

1. A RESINOUS REACTION PRODUCT PRODUCED BY HEAT REACTING (I) MALEIC ACID AND (II) MATERIAL LIQUID AT 325*F. AND SELECTED FROM THE GROUP CONSISTING OF (A) ORGANIC REACTION MASSES PRODUCED BY REACTING FURFURALDEHYDE AND A KETONE HAVING AT LEAST TWO HYDROGEN ATOMS ON AN ALPHA CARBON, AT LEAST 5% BY WEIGHT OF EACH OF SAID REACTION MASSES BEING A RESINOUS MATERIAL, (B) RESIDUES OF (A) PRODUCED BY HEAT DISTILLATION OF (A) AND MEASURED BY WEIGHT AT LEAST 10% OF (A), (C) MONOFURFURYLIDENEKETONE, (D) DIFURYLIDENE-KETONE, (E) HOMOPOLYMERS OF (A)-(D) RESPECTIVELY, (F) PARTIALLY HYDROGENATED HOMOPOLYMERS (E), REACTION MASSES (A) AND RESIDUES (B), RESPECTIVELY, (G) PARTIALLY HYDROGENATED MONOFURFURYLIDENEKETONE, (H) PARTIALLY HYDROGENATED DIFURFURYLIDENE-KETONE, (I) RESIDUES OF PARTIALLY HYDROGENATED (A), SAID RESIDUES PRODUCED BY THE HEAT DISTILLATION THEREOF AND MEASURING BY WEIGHT AT LEAST 10% AND PREFERABLY 60% THEREOF, (J) HOMOPOLYMERS OF (F)-(I) RESPECTIVELY, SAID (F), (G) AND (H) PRODUCED BY PARTIALLY HYDROGENATING MATERIALS (A)(E) RESPECTIVELY TO SATURATE THEM WITH HYDROGEN TO THE EXTENT EQUAL TO APPROXIMATELY 15%-65% OF THAT REQUIRED TO SATURATE ALL OF THE CARBON TO CARBON DOUBLE BONDS IN SAID MATERIALS (A)-(E). 